This chapter explains how the principles of chemical thermodynamics are used in the construction and interpretation of phase diagrams. After a brief review of the laws of thermodynamics, it describes the concept of Gibbs free energy and its application to transformations that occur in single-component and binary solid solutions. It then examines the relationship between the free energy of a solution and the chemical potentials of the individual components. It also explains how to account for the heat of mixing using quasi-chemical models, discusses the effect of interatomic bond energies and chemical potentials, and shows how the equilibrium state of an alloy can be obtained from free-energy curves.

Phase diagrams are graphical representations that show the phases present in the material at various compositions, temperatures, and pressures. This chapter begins with a section describing the construction of phase diagrams for the simple binary isomorphous system. A binary phase diagram can be used to determine three important types of information: the phases that are present, the composition of the phases, and the percentages or fractions of the phases. The chapter then describes the construction of one common type of binary phase diagram i.e., the eutectic alloy system. The major eutectic systems include the aluminum-silicon eutectic system and the lead-tin eutectic system. The chapter discusses the construction of eutectic phase diagrams from free energy curves. It also provides information on peritectic, monotectic, and solid-state reactions in alloy systems. The presence of intermediate phases is also described. Finally, a brief section provides some information on ternary phase diagrams.

This chapter provides a short introduction to phase transformations, namely, the liquid-to-solid phase transformations that occur during solidification and the solid-to-solid transformations that are important in processing, such as heat treatment. It also introduces the concept of free energy that governs whether or not a phase transformation is possible, and then the kinetic considerations that determine the rate at which transformations take place. The chapter also describes important solid-state transformations such as spinodal decomposition and martensitic transformation.

This chapter explains the significance of the phase diagram and its use in the development of new materials. The chapter describes the basic rules of heterogeneous equilibrium, presents a comparison between liquidus line and solidus line, and provides information on the solubility curve and the binodal curve.

This chapter describes the physical characteristics, properties, and behaviors of solid solutions under equilibrium conditions. It begins with a review of a single-component pure metal system and its unary phase diagram. It then examines the solid solution formed by copper and nickel atoms. It discusses the difference between interstitial and substitutional solid solutions and the factors that determine the type of solution that two metals are likely to form. It also addresses the development of intermediate phases, the role of free energy, transformation kinetics, liquid-to-solid and solid-state phase transformations, and the allotropic nature of metals.